Process of preparing alkyl ethers of 3&#39;-nitro 4&#39;-hydroxy ortho-benzoyl benzoic acid



c ITE y "teaser Saree .ATE, "or'FIc IVAN GUBELMANN, HENRY a. wiaI'LANi), AND M0 sT fiLMANmbF some MILWAU v KEE, WISCONSIN, ASSIGNORS TO THE WISCONSIN, A CORPORATION OF DELAWARE.

NEWPORT COMPANY, OF CARROLLVILLE,

, PRooEss'or rnnranme ALKYL mamas or a m'rao r-HYimoxY omHo-BENzoYL c BENZOIC ACID. v

'NoDrawing. Application filed June 28,

I This invention relates to a process of preparing alkyl ethers of 3-nitro 4-hydroxy ortllo benzoyl-benzoic arid and to the alkyl ethers thus prepared.

e have discovered that. nlky-l ethers of 3-nitro .4-hydroxy ortho-benzoyl-benzoic acid can be-preparcd from 3-nitro 4-chloro ortbo-benzoyl-benzoic acid by treating it or 4 itsalkali salts with an alcohol and a caustic alkali,- such as caustic soda or caustic pot i I Cl oooM It is obvious that other halogen derivatives than the chlorine derivative may be em-; ployed, but because of its availability and cheapness the chlorinederivative is preferred.

These ethers form at various reaction temperatures, at room temperature very slowly and at the boiling point of the reaction mixture more rapidly. The amount of alkali used-forthis reaction is approximately one and one-half molecular weights to one molecular weight of the 3-nitro y-chloro-ortho benzoyl benzolc ac1d salt, or two and onehalf molecular weights of the alkali to one V containing ammonia, but are practically insoluble indilute mineralacidsf The alkaline solutions of the ethers are of a deep yellow color and the ethers can be-precipitated from these alkaline solutions by the addition of common salt or an excess of alkali or by the addition acid, in the first two 1926. Serial No. 119,246; 7'

ash. This reaction has been carried out using methyl alcohol and ethyl alcohol, giving the corresponding ethers; The reaction proceedsnccording to the following equation, in which R represents l'n'ethyl, ethyl or any other alkyl radical and in which M may represent so-dium or potassium or any other metal capable of forming a soluble salt in alcohol with 3-xiitro 4-chloroortho-benzoyl-benzoic acid.

on i 7 coon casesthe corresponding alkali salts beingprecipitatedl and in the third case, the free acid. Upon boiling the alkaline solutions, the others are transformed into 3-nitro'thydroxy ortho-benzoyl-benzoic acid, the preparation of which is described in our copending application, ff3'-nitro 4-hydroxy m-tho-benzoyl benzoicacid and a process of making the same, executed of even date herewith. I

Without limiting our invention to any particular procedure, thef following examples llustrate the application of our invention in the preferred form:'

. Methyl ethri To 610 parts'by weight of methyl alcohol of 90% strength by Weight, are added 305 parts by weight of 3-nitro 4J-chloro-ortho-benzoyl-bcnzoic acid. The mixture is heated to 40 C. and a caustic soda solution, made up of 500 parts by volume of methyl alcohol of 90% strength by weight and-l00 parts by weight of caustic soda, added over a period of 4 to 5 hourg-keeping theteniperat'ure at all times at 4 0f.C. The reaction'isth'en regarded as finished .and'thq mass isheutral-ized by the addition of about 200 parts by weight of hydrochloricmcid 20 B, Th alchohol is then distilled off, ma'intaiping the volume of the original re-- en the mass is free of alcohol, it iscooled r I 'to 20 (3., diluted with 2000parts by weight of cold water and filtered. The cake, which is the 3 -nit ro-etf-methoxy-ortho-benzoyl-bcnzoic acid, is dried at 100 C. The yield is close to that expected theoretically and the crude product-melts at 182 to 184 C. The crude product may be purified by recrystallizing it from dilute methyl alcohol, after which operation the melting point rises to 188 to 189 C. Y

Ethyl ether.

In 2500 parts by volume of ethyl alcohol, 80% by weig t, are dissolved HOparts by weight of potassium hydroxide. To this ded 305 parts by weight of 3.-nitro i chloro- 'ortho-benzoyl-benzoic acid. The, mass -is now heated up slowl over a period ofto 4.0 minutes, to 60 The reaction is now. considered completed and the reaction mass ,is neutralized with about 200 parts by weightof hydrochloric acid, 20 B. After diluting to a total volume of 5000 partsvby volume with hot water, the mass is cooled. to 20 (1, and filtered. The recipitated crystals aiter filtration are'drie at 100C.

e melting point on this product is 160 to 162 C. Upon further purification from dilute alcohol, the melting point rises to 164 to 165 C. The yield is close to that expected theoretically.

We are aware that numerous details of the process may be varied without departing from the spirit ofthis invention, and

, we do not desire limiting the patent granted other than as necessitated by the prior art.

We claii 1 as our invention l. The process of preparing 3-nitro 4- alkyl-ether ortho-benzoyLhenzoic acid, which I, comprises treating 3-nitro 4=-ha logen-orthobenzoyl-benzoic acid with an alcohol in'the presence of an alkaline reacting substance.

2. The process of preparing 3-nitro 4; alkyl-ethcr-ortho-benzoyLbenzoic acid, which comprises treating 3-nitro i-chlor'o-orthobenzoyl-benzoic acid with an alcohol in the presence of caustic alkali.

3. The process of preparing 3 -nitro-ftmcthoxy-ortho-benzoyl-benzoic acid, \VlllCll comprises heating 3-nitro 4'-chloro-ortho-' benzoyl-benzoic acid with methyl alcohol in' the presence of caustic alkali.

4. The process of pre aring 3-nitro 4- alkyl-ether-orthosbenzoylenzoic acid, which comprises treating 3'-nitro 4-'chloro-orthobenzoyl-benz'oic acid with 3I1-,2ll00ll0l in the presence of an alkaline reacting substance.

5. The process of preparing 3n-itro 4'- alkyl-ether-ortho-benzoyl-benzoic acid, which comprises reacting upon 3-nitro 4.--chloro- V ortlio-benzoyl-benzoic acid with an alcohol in thc presenceof caustic alkali, the alkali being-in the proportion of two and one half molecular weights to one molecular weight of the free .acid. 1 v

6. The process of preparing 3"-nitro 4:- alkyl-ether-ortho-benzoyl-benzoic acid which comprises reacting upon 3-nitro 4-chl'or0- ortho=benzoyl benzoic acid-and its salts with an alcohol in the presence of caustic alkali,

neutralizing and filtering out the 3-nitro 4'- alkylether-ortho-benzoy l-benzoic acid. 7. As a new article of manufacture, al-kyl others of 3-nitro 4'41 'drox -ortho-benzo 'lsolution at a temperature of 20 C. are ad 1, 3 y 3 enaoic acid, having most probably the following formula:

con

wherein R represents any alkyl group such as methyl, ethyl and the like and M represents a hydrogen or metal atom.

8 As a new article of manufacture, 3'- nitro 4'-methoxy-ortho-benzoyl-benzoic acid, having most probably the following formula:

OCH:

in which M represents a hydrogen or metal atom.

'9. The processot' preparing 3-nitro 4- alkyl-ether-ortho benzoyl benzoic acid, which comprises reacting upon 3-nitro 4-halogenortho-benzoyl-benzoic acid with an alcohol in the presence of caustic soda.

In testimony whereofwehave hereunto subscribed our names.

YIVAN' GUBELMANN.

HENRY J. WEILAND. o'r'ro STALLMANN.

coon i 

